Reagents from phenolic and 8-hydroxyquinolinic aldehyde oximes

ABSTRACT

A process for producing reagents useful in organic synthesis, for removing metal values from solutions thereof, for the capture of aldehydes, of the general formula ##STR1## wherein Z designates a recurring part (CH 2  --CH--CH 2 ) of a polymeric backbone of a polymer like polystyrene, of a copolymer comprising polystyrene and divinylbenzene, and butadiene, or other copolymers comprising styrene moieties; or wherein Z is the aliphatic moiety of a long-chain aralkyl compound having a terminal aryl group; or wherein Z designates alkyl; corresponding compounds wherein instead of the optionally substituted phenyl group there is present an optionally substituted naphthyl group; wherein n is an integer of from 1 to 15, and wherein Q designates a group selected from: ##STR2## wherein R designates --H, lower alkyl, aryl, which may be substituted and wherein R&#34; designates --H, alkyl, aryl, halogen, nitro or carboxy, or ##STR3## wherein R is --H, lower alkyl, aryl (which may be substituted), R 1  is --H, alkyl, aryl (which may be substituted), R 2  is --H, alkyl, aryl or substituted aryl, and wherein Y is --H or a non-interferring substituent, which comprises chemically binding an activated chemical moiety to a group ##STR4## or a corresponding naphthyl-containing group, wherein Z is as defined above, according to the reaction scheme: ##STR5## wherein Q is as defined above, or a functional group which can be converted to such group after the chemical bonding; and X is --Cl or --Br.

This is a division, of application Ser. No. 545,220, filed Jan. 29, 1975now U.S. Pat. No. 4,085,261.

The present invention relates to novel ion exchange agents and to aprocess for preparing these. Various polymeric substances were preparedhitherto, which contain certain desired functional moieties, adapted tocarry out a specific activity. According to the methods used hitherto,such polymeric agents are prepared by a sequence of steps, and generallythere take place certain undesired side-reactions, which result incross-linking side-reactions and in undesired physical properties of theproducts. It is stressed that the novel process of the present inventionresults in substantially improved products, which have advantageousphysical and chemical properties. The advantageous properties of theproducts obtained according to the present invention are a direct resultfrom the method of preparation of the ion-exchange agents. It is one ofthe main features of the present invention to prepare the novelion-exchange resins by activating a comparatively small molecule,carrying the desired chemical function, and to attach this to thepolymer backbone of a predetermined polymeric carrier. The activation ofthe small molecule and its chemical bonding to the polymer substantiallyeliminates undesired side-reactions, and the product is obtained in amuch improved form and has an enhanced degree of activity andspecificity compared with similar agents prepared by the conventionalsequence of reactions.

The products according to the present invention can be obtained in solidor in liquid form, as desired for certain specific purposes. There maybe used a solid polymer backbone, or there may be used long-chainaliphatic compounds having a terminal functional group as carrier, andin the latter case liquid products are obtained.

The novel ion-exchange agents according to the present invention may beused for a wide variety of uses, depending on the functional moietiesbuilt into the molecule. They are effective agents for carrying outcertain chemical reactions, such as acylations and the like; certain ionexchangers are effective agents for the selective removal of certainmetal values from solutions of same; some may be used as ion exchangemembranes, etc. Some of the products based on long-chain compounds canbe used for liquid/liquid extractions, as their solubility in aqueoussolutions is a very low one. Other and further features of the presentinvention will become apparent from the following description.

In our copending U.S. application Ser. No. 511,687, now U.S. Pat. No.3,974,110, there is described and claimed a process for preparingcertain reagents useful for effecting reactions of organic synthesis, ofthe general formula ##STR6## wherein

Z designates the ##STR7## part of a polymeric backbone of a polymer likepolystyrene, a copolymer comprising polystyrene and a comonomer likedivinylbenzene, butadiene and other copolymers comprising styrene; orthe aliphatic moiety of a long-chain aralkyl compound having a terminalphenyl or alkyl;

n is an integer of from 1 to 8, inclusive,

R designates oxygen or sulfur;

X designates nitro, carbonyl, carboxyl, cyano-carbalkoxy or acarboxamido group which may be substituted on the nitrogen atom, or ahalogen atom, wherein Y is -H or a non-interfering substituent, andcorresponding compounds with a naphthyl group instead of the ##STR8##

The present invention relates to the preparation of further reagents ofsimilar structure, but which are useful for certain uses notcontemplated in our said first patent application.

The novel products of the present invention are prepared by chemicallybinding an activated chemical moiety to a polymer backbone, the term"polymer backbone" designating a solid polymer or a long-chain compound.The reaction can be schematically represented, by the reaction sequence##STR9## Wherein P designates the polymeric backbone as hereinbeforedefined, which in the case of solids can be a polystyrene polymer of thetype ##STR10## or a similar copolymer, such as for example with 2%D.V.B. or in the case of liquids it designates a long-chain compound,such as for example dodecyl benzene or the like, of the formula##STR11## In the above X designates halogen such as --Cl --Br or --OH or--OR and R--CH₂ -- designates the desired functional moiety attached tothe polymer backbone.

Weak acid and weak base ion exchange resins can be prepared by reactinga polymeric backbone, as defined above, with a chloromethylatedchloro-nitro-benzene or with chloromethylated nitrobenzene,respectively, as shown schematically in the following reaction sequence:##STR12##

The above weakly acidic or weakly basic agents can be used as ionexchange resins.

Chelating Agents

Non-selective ion exchange agents according to the present invention canbe converted into effective chelating agents by means of the Friesrearrangement: ##STR13##

The 8-hydroxy-isoquinoline polymer can be esterified as above, and afterthe Fries rearrangement and conversion to the oxime there are obtainedpolymeric chelating agents useful in the removal of the recovery ofmetal values from solutions. The reaction sequence is schematically asfollows: ##STR14##

A further type of reagent was prepared by the reaction sequence set outin the following: ##STR15## wherein

R₁ designates --H, alkyl or aryl;

X designates alkyl, aralalkyl, halogen, nitro, carboxyl, carboxaldehyde

R" designates --H, alkyl or aryl including substituted aryls.

Similar polymeric agents were prepared by conventional methods and itwas found that the ones prepared by the reaction sequence according tothe present invention had a higher degree of activity as evident fromloading characteristics of the resin, (See U.S. Pat. No. 3,974,110) andthat the physical shape and stability of the agents according to thepresent invention was much better. They were used for repeated sequencesof metal removal and were found not to deteriorate.

EXAMPLE 1: 4-Nitrobenzylated Polystyrene

To a solution of 1.3 g aluminum chloride in 10 ml nitrobenzene there wasadded 1.7 g 4-nitrobenzyl chloride and 2 g of Xe-305 (polystyrene inbead dorm, Rohm & Haas, USA). The mixture was maintained at atemperature of 65° C. during 72 hours. At the end of this period of timethe product was poured on 20 ml of a methanol/HCl mixture (1:1, Conc.HCl), washed with 20 ml of methanol and dried at 80° C. during 5 hours.A crop of the desired product of 3.0 g was obtained. It had a nitrogencontent of 4.53% by weight.

EXAMPLE 2: 4-Aminobenzylated Polystyrene Hydrochloride

To a solution of 14 g stannous chloride hydrate in 20 ml ethanol and 20ml concentrated aqueous hydrochloric acid there was added 3 g of thepolymer obtained in Example 1. The mixture was maintained at atemperature of between 80°-90° C. during 20 hours, the resin wasfiltered off, washed with a warm mixture (1:1) of ethanol and conc. HCl,with 1 N HCl, with water and with acetone. The product was dried, andthe nitrogen content was 4.59% and chlorine content was 6.35% by weight.

EXAMPLE 3: 4-Isocyanato-benzylated Polystyrene

The product of Example 2 was reacted in its hydrochloride form withphosgene at 60°-70° C. for 2 hours. The phosgene was driven off with astream of nitrogen, the polymer was filtered off and washed with dryether. A quantitative yield of the desired product was obtained.

The polyiscyanato substituted polymer reacts quickly with nucleophiles.Thus, for example, 2 g of the polymer eliminated quantitatively 1 mmolebenzylglycine from a solution thereof in 10 ml chloroform.

The polyisocyanato polymer was reacted with hydrazine (2 g of thepolymer with 2 g hydrazine in dioxan during 1 hour), yielding aquantitative yield of the corresponding semicarbazide. Analysis:nitrogen: 7.05%; chlorine: 0.51% (residual).

EXAMPLE 4: (3-Nitro-4-chloro) benzylated Polystyrene

To a solution of 10.4 g aluminum chloride in 120 ml nitrobenzene therewas added 19.1 g 3-nitro-4-chloro benzylchloride followed by 16 g ofXe-305 resin, and the mixture was maintained at 90° C. during 3 days.The resin was poured on a methanol/hydrochloric acid (1:1, conc. Hcl)mixture, washed with methanol, with dimethyl-formamide, methanol, andwith water. A crop of 20.7 g of dry product was obtained having anitrogen content of 1.82% by weight.

EXAMPLE 5: (3-Nitro, 4-hydroxy; 5acetyl)benzylated Polystyrene

5 g (3-nitro, 4-hydroxy) benzylated polystyrene cross-linked with 2%divinylbenzene of mesh size 200-300 was converted into the acetate byleaving in a solution of excess acetic anhydride and pyridine in 50 mlmethylene chloride until the resin lost its yellow color. It wasfiltered off, washed with methylene chloride and desiccated overnightover phosphorus pentoxide under a high vacuum. The thus obtained(3-nitro, 4-acetoxy) benzylated polystyrene was left in a solution of1.3 g aluminum chloride in 25 ml nitrobenzene at 65° C. for 24 hours.The product was poured on a methanol/hydrochloric acid mixture (1:1,conc. Hcl), filtered off, washed with methanol, with water, withmethanol and dried. The yellow product shows a carbonyl at 1695 cm⁻¹.

By the same procedure a similar resin was prepared, starting withmacroporous Xe-305. It had a nitrogen content of 2.55% by weight.

EXAMPLE 6: (8-Hydroxy-quinoline)-5-benzylated Polystyrene (not part ofthe invention)

2 g of dry chloromethylated polystyrene (Xe-305) were reacted with 1.2 gof 8-hydroxyquinoline and 1.35 g aluminum chloride in 20 ml nitrobenzeneat 70° C. for 20 hours, during which time the hydroxyquinolinedissolved. The resin as filtered off, washed with methanol: withhydrochloric acid (1 N), with sodium hydroxide (0.5 N), with water, withacetone and dried. There was obtained a crop of 2.0 g of the desiredproduct which had a nitrogen content of 2.4% by weight.

EXAMPLE 7: (8-Hydroxy-quinoline)-5-benzylated Polystyrene

According to a preferred embodiment, there are reacted 2.5 g aluminumchloride. 2.4 g 5-chloromethyl-8 hydroxyquinoline and 2.0 g of Xe-305polystyrene resin in 10 ml of nitrobenzene. The reaction was carried outat 60° C. and during 20 hours. The resulting resin was filtered off,washed with HCl/methanol (1:1, conc. Hcl), with methanol, water,methanol and ether. The dry product had a nitrogen content of 1.79%. Acrop of 3.0 g was obtained.

The resulting 8-hydroxyquinoline resins can be loaded with amino acidsand this can be used for the synthesis of peptides. 1.1 g of the polymerobtained in the present example in its hydrochloride form was reactedwith 10 ml of a solution of 5%, triethylamine in chloroform until itlost its yellow color, filtered off, washed three times with chloroformand introduced into a solution of 0.8 g BOC-alanine in 25 mldimtehylformamide. The reaction mixture was cooled to 0° C., 0.8 gdicyclohexylcarbodiimide (DCC) was added and left to stand overnight.The resin was filtered off, washed and dried. The loading, as determinedby the benzylamine method, was 0.7 mmole/g.

A comparison of the resins obtained according to Examples 6 and 7 showsthat the resin obtained according to Example 7 is mechanically stableand colorless after neutralization while that of Example 6 is coloredand decomposes upon prolonged storage.

EXAMPLE 8: (4-hydroxy, 3-acetyl) benzylated Polystyrene

To a solution of 1.8 g aluminum chloride in 100 ml nitrobenzene therewas added 2 g of Xe-305 polystyrene polymer; the reaction mixture wasbrought to 60° C. and during 48 hours there was added dropwise aquantity of 1.8 g 2-acetyl-4-chloromethyl phenol in 100 ml nitrobenzene.After stirring for additional 20 hours the polymer was poured into HCl(2 M), filtered off, washed with methanol, with water, with methanol anddried. A crop of 2.4 g of the desired product was obtained, having acontent of 1 mmole -OH groups/g polymer; IR absorption at 1640 cm⁻¹,(KBr).

EXAMPLE 9: (2,6-Dichloro-3-acetyl-4-hydroxy) and(2,4-dichloro-5-hydroxy-6-acetyl) benzylated Polystyrene

To a solution of 1.7 g aluminum chloride in 10 ml nitrobenzene there wasadded 2.3 g of chloromethyl-2,4-dichloro-6-acetyl phenol (isomericmixture) and 2.0 g Xe-305 resin. The mixture was kept at 70° C. for 48hours, poured on hydrochloric acid (2 M) and the resin was filtered off,washed with methanol, with water, with methanol and dried. A quantity of2.35 g of the desired product was obtained.

EXAMPLE 10: 3-Nitro-4-hydroxy-benzylated toluene.

1 Millimole of 3-nitro-4hydroxy-benzyl chloride was reacted with excessof toluene in 1.8 M aluminum chloride in 20 ml of nitrobenzene at 65° C.for 20 hours. The product was diluted with toluene and washed withhydrochloric acid (1 N), water, and the nitrobenzene was removed bysteam distillation leaving an oily substance which crystallized uponstanding. IR: 1690 cm⁻¹ ;

NMR: 2.3 ppm (3H) absorption of methyl; 4.2 ppm (2H) absorption ofmethylene.

EXAMPLE 11: 3-Nitro, 4-hydroxy-benzylated Dodecylbenzene,

6.2 g (25 mmoles) dodecylbenzene and 5.7 g of 3-nitro-4-hydroxybenzylchloride were reacted with 3.6 mmoles aluminum chloride in 20 mlnitrobenzene as set out in Example 10. There was obtained a yield of 8.9g of an oily substance. The IR and NMR spectra were in accordance withthe expected formula.

Example 12: (8-Hydroxyquinoline)-5-benzylated cyclododecylbenzene.

1 g 5-Chloromethyl-8-hydroxyquinoline and 1 g cyclododecylbenzene werereacted with 1 g aluminum chloride in 10 ml nitrobenzene at 60° C.during 3 hours. After dilution with 40 ml of chloroform the product waswashed with water, the chloroform was removed and the productcrystallized from nitrobenzene. There was obtained 1.2 g of yellowcrystals. The NMR and IR spectra confirm the expected formula.

EXAMPLE 13: Preparation of Benzhydroxytriazole Polymer Stage A

10 g of Xe 305 polystyrene were added to 13 g 3-nitro-4-chlorobenzylalcohol and 10 g aluminum chloride in 50 ml benzene. The reactionmixture was left at 70° C. for 3 days, poured on ice-water washed withmethanol, hydrochloric acid (1 N), methanol, and dioxan and the productwas dried. There was obtained 14.3 g of a colorless polymer containing7.0% chlorine.

Stage B

10 g of the product of Stage A were refluxed in 40 ml hydrazine hydrate(98%) and 60 ml 2-ethoxyethanol. The reflux was effected during 1 hourand after this period the polymer was filtered off, washed with water,with dioxan, methanol, ether and dried. The product contains 0.4% Cl,and 5.4% nitrogen.

Stage C

The product of Stage B was mixed with 50 ml concentrated hydrochloricacid and 50 ml dioxane and stirred at room temperature for 20 hours. Thepolymer was filtered off, washed with water, dioxan, methanol, ether anddried. The desired benzhydroxytriazole polymer (BHT) was obtained inquantitative yield. Nitrogen content: 5.2%

Example 13: A. Triphenylmethyl Polymer

A quantity of 5 g polystyrene (Xe 305 Rohm & Haas) was reacted with 10 gbenzhydrol in a 1.8 M solution of aluminum chloride in nitrobenzene (20ml). The reaction was carried out at 75° C. during 20 hours. Thereaction mixture was worked up as in Example 1 and there was obtained0.9 g of the desired product, 2 mmole/g of the polymer.

B. 4-Chlorobenzylated Polystyrene

In a similiar manner, 5 g of polymer were reacted with 5 g ofchlorobenzyl chloride to give 6.6 g of 4-chlorobenzylated polystyrenecontaining about 2 mmole chlorine per gram of polymer.

C. Polypyridine Polymer

A quantity of 1.2 g of 3-pyridyl carbinol in 15 ml of 1.8 M aluminumchloride in nitrobenzene was reacted with 2 g Xe-305 during 3 days at80° C. The polymer was poured on methanol, filtered off and washed withHCl methanol, aqueous methanol, methanol and ether. A crop of 2.6 g ofthe desired product was obtained which contained 3.6% nitrogen.

D. 3-Pyridyl Tolylmethane

A quantity of 1.2 g 3-pyridyl carbinol in 15 ml 1.8 M aluminum chloridein nitrobenzene was reacted with 10 ml of toluene during 3 days at 80°C. The reaction mixture was poured on HCl/ice and extracted withtoluene. The organic phase was washed with water, dried and the solventwas evaporated. The desired product was obtained as viscous oil,containg 8.5% nitrogen.

E. 4-Hydroxy-3-formyl Benzylated Polystyrene

The preparation was carried out as in Example 8, but with2-formyl-4-chloromethyl phenol.

F. 4-Hydroxy-3-formyl benzylated Toluene.

The preparation was according to Example 8 and a similar yield of thedesired product was obtained.

EXAMPLE 14: Fries Rearrangement of Phenol Esters.

The acetoxy derivatives of the phenols were prepared by leaving them ina methylene chloride solution of acetic anhydride (from 1:1 to 1:2), andpyridine (1 to 10%), until decolorization has taken place. The resinswere filtered off, and washed with methylene chloride. The liquids werewashed with water, concentrated hydrochloric acid, water, and thesolvent was evaporated. The samples were left in a dessicator undervacuum, over phosphorus pentoxide, for a period of 20 hours. Otheresters were prepared in a similar manner.

The rearrangement was effected at a temperature in the range of between45°-100° C., preferably at about 65° C., by leaving the esters in anitrobenzene solution of aluminum chloride. Good results were obtainedwith a 1.8 M aluminum chloride solution by leaving for about 20 hours.The resulting polymers were filtered off, washed with methanol,concentrated hydrochloric acid, methanol and ether.

The liquids were diluted with ether (about 5 ml per 1 ml of liquid),washed with concentrated hydrochloric acid, water and the solvent wasevaporated. All the liquid products could be identified by the presenceof acetylic hydrogens in the NMR spectra. The acetylic hydrogens were inthe region of 2.0-25 ppm and there exists the typical shift of the 1750cm⁻¹ acetoxy absorption to the 1690-1700 cm⁻¹ aromatic ketoneabsorption. In addition the corresponding oximes and dinitrophenolderivatives were prepared. The following acylated derivatives wereprepared:

(3-Nitro-4-hydroxy-5-acetyl) benzylated polystyrene of both the 2%D.V.B.-polystyrene type, and Xe-305.

Oxime: % N 2.7; DNP: % N 5.4

(3-Nitro-4-hydroxy-5-acetyl) benzylated toluene

(3-Nitro-4-hydroxy-5-acetyl) benzylated dodecylbenzene

5-(7-Acetyl-8-hydroxyquinoline) benzylated polystyrene

5-(7-Acetyl-8-hydroxyquinoline)-benzylated cyclododecylbenzene

(3-Nitro-4-hydroxy-5-benzoyl) benzylated polystyrene

(3-Nitro-4-hydroxy-5-p-nitrobenzoyl) benzylated polystyrene

EXAMPLE 15: Preparation of Oximes

The oximes were prepared starting with the acylated polymers (containingabout 4 mmole acyl groups per 2 g of polymer). These were refluxed withhydroxylamine hydrochloride. Good results were obtained by using 10 mlof an ethanolic solution containing 1.4 ml (10 mmole) triethylamine and0.7 g (10 mmole) hydroxylamine hydrochloride and the reflux was effectedduring 20 hours. The polymer was filtered off, washed with warm ethanol,with dilute acid and with water.

Liquid oximes were prepared by the same procedure; the product was takenup in benzene, washed with dilute acid and with water. Upon evaporationof the solvent, the desired products were obtained as oily substance.

The products showed the typical IR-absorption in the region of 1660-1640cm⁻¹ with the disappearance of the carbonylic band at 1690 cm⁻¹.

In this manner the following oximes were prepared:

A. Oxime of (3-Nitro-4-hydroxy-5-acetyl) benzylated polystyrene (Xe-305polymer: analyses 4.28% N).

B. Oxime of (3-Nitro-4-hydroxy-5-acetyl) benzylated dodecylbenzene (1.8%N).

C. Oxime of (7-Acetyl-8-hydroxy-quinoline)-5-benzylated polystyrene)(analysed 2.74% N).

D. Oxime of (4-Hydroxy-3-acetyl) benzylated polystyrene (analyses 1.61%N).

E. Oxime of (2,6-dichloro-3-acetyl-4-hydroxy and(2.4-dichloro-5-hydroxy-6-acetyl) benzylated polystyrene (analyses 1.28%N).

F. Oxime of (7-Acetyl-8-hydroxyquinoline) benzylatedcyclododecylbenzene.

G. Oxime of (4-hydroxy-3-acetyl) benzylated dodecylbenzene.

H. Oxime of (4-hydroxy-3-Formyl) benzylated dodecylbenzene.

I. Oxime of (4-hydroxy-3-formyl) benzylated polystyrene.

EXAMPLE 16: Extraction of Metals.

The following aqueous solutions were tested:

a. 2.1 g/l Cu as copper sulphate, 0.5 M Na₂ SO₄, pH 1.3

b. 2.1 g/l Cu as copper sulphate, 0.5 M Na₂ SO₄, pH 2.12

c. 2.1 g/l Cu as copper sulphate, 0.5 M Na₂ SO₄, pH 2.72

d. 1.525 g/l CuSO₄ ; pH 2.42

0.22 g/l Cu(NH₃)₄ SO₄, PH 9.5

f. 2.1 g/l FeCl₃, pH 2.8

g. 1.45 g/l FeCl₃ in conc. phosphoric acid

The extraction was effected by shaking the solutions for 2 minutes in aseparatory funnel with solutions of the reagents in chloroform at 1:1ratio. The phases were separated and the organic phase was washed with0.01 N sulfuric acid. After this the stripping was effected by means of2 M H₂ SO₄ at a 1:1 ratio (by volume). The results are given in TableNo. 1. The analysis was by means of atomic absorption spectrometry.

Solutions (d) and (e) were used for copper, (f) and (g) for iron. Thetests were conducted as follows: a resin bed was prepared by insertingabout 2 g of dry resin into a column of 10 mm diameter. The solutionswere passed at a rate of 1 ml/minute, the resin was washed with 0.01 NH₂ SO₄ and then stripped by means of 2 M H₂ SO₄. The results are givenin Table No. 2.

    ______________________________________                                        Reagent                                                                              % of     No. of                                                        Ex. No.                                                                              reagent  solution A:O    pH    % Extraction                            ______________________________________                                        15/F   5        a        1:1    1.3   76                                      15/F   5        b        1:1    2.12  81                                      15/B   5        a        1:1    1.3   90                                      15/B   5        b        1:1    2.12  100                                     15/B   5        e        1:1    9.5   99                                      15/G   8        d        1:2    2.42  30                                      15/G   8        e        1:1    9.5   100                                     15/G   8        f        1:1    2.8   0                                       15/H   6        d        1:2    2.4   12                                      15/H   6        e        4:1    9.5   57                                      15/H   6        f        1:1    2.8   0                                       21/d   5        a        1:1    2.4   88                                      21/d   5        a        5:1    2.4   88                                      21/d   5        e        5:1    9.5   10                                      ______________________________________                                    

                  TABLE 2:                                                        ______________________________________                                        Absorption of Copper and Iron                                                 by Chelating Resins                                                           Resin acc. to                                                                 Example No.                                                                            Metal    Solution pH    Loaded mg/g resin                            ______________________________________                                         7       Cu       d        2.42  12                                           7        Fe       f        2.8   3                                            7        Fe       g              0.6                                          15/C     Cu       d        2.42  6.3                                          15/C     Cu       e        9.5   9.7                                          15/C     Fe       f        2.8   1.1                                          15/A     Cu       d        2.42  0.2                                          15/A     Cu       e        9.5   5.3                                          15/A     Fe       f        2.8   0.9                                          15/i     CU       d        2.42  0.7                                          15/i     Cu       e        9.5   11                                           15/i     Fe       f        2.8   1.2                                          15/D     Fe       g        --    --                                           15/D     Cu       d        2.42  0                                            15/D     Cu       e        9.5   5                                            ______________________________________                                    

EXAMPLE 17: Kinetics of Resin Loading and Elution

The resin used was that prepared according to Example No. 7 A quantityof 1 g of the resin was stirred in 10 ml of Solution (d) of Example 16,at a pH of 2.42. Aliquots were removed and tested. The resin was thenseparated and stripped by means of 10 ml 2 M sulfuric acid.

                  TABLE 3:                                                        ______________________________________                                        Rate of Absorption and Elution                                                            Loading         Stripping                                         Time (min)  Conc. of Solution                                                                             (ppm)                                             ______________________________________                                        1           830             --                                                5           570             900                                               10          --              910                                               15          450             960                                               25          --              1120                                              Loaded: 9 mg total stripped 11.2                                              Resin: Ex. No. 7                                                              ______________________________________                                    

A quantity of 2 g resin prepared according to example 7 was stirred in100 ml of Solution (e) of Example 16 of pH 9.5. The stirring was carriedout as indicated and after this period of time the resin was washed andstripped with 10 ml of 2 M sulfuric acid. The results are given in Table3:

                  TABLE 3:                                                        ______________________________________                                        Time       conc. (ppm) in solution                                            (min)      Loading        Stripping                                           ______________________________________                                        0          220            --                                                  13         --              970                                                5          --             1050                                                6          190            --                                                  10         --             1200                                                15         150            --                                                  50         110            --                                                  ______________________________________                                    

EXAMPLE 18: (8-Hydroxyquinoline)-5-Benzylated Toluene

The preparation was effected as in Example 7, but starting with 20 mltoluene instead of 2.0 g of Xe-305.

The work-up was as follows: Water was added, the organic phase waswashed with water, dried and after this excess of solvent was removedunder reduced pressure.

EXAMPLE 19: (4-Hydroxy-3-acetyl) Benzylated Toluene

The preparation was as in Example 8, but starting with 20 ml of toluene.The reaction mixture was worked up as in the preceding example.

EXAMPLE 20: Extnaction of Uranylsulfate with 3-pyridyl-tolylmethane

A solution was prepared, containing 5 g of the above reagent per 100 mltoluene. The thus obtained solution was used at a volume ratio of 1:1 toextract U₃ O₈ from an aqueous solution of same containing 1 g/l uranylsulfate. The extraction was at a pH of 2.0 and 80% of the uranyl ionswere extracted.

Example 21

In a manner similar to that of Example 15, the oximes of the compounds

a. (4-hydroxy-3-formyl) benzylated polystyrene;

b. (4-hydroxy-3-formyl) benzylated toluene;

c. (8-hydroxyquinoline) 5-benzylated toluene and of

d. (4-hydroxy-3-acetyl) benzylated toluene

were prepared.

Solutions of the compound of Example 21(d) were used for extractingmetals according to Example 16. A 5% solution of the reagent was used.

With Solution a, at a A:O ratio (defined in Example 16) of 1:1 at pH 2.4an extraction of 88% was obtained.

The same system, but at A:O of 5:1 gave the same extraction.

Solution No. 5 at an A:O ratio of 5:1 at pH 9.5 gave an extraction of100%.

We claim:
 1. A chelating agent of the formula ##STR16## wherein Z isalkyl or aralkyl, the aliphatic portion of which being long-chain alkyland the aryl portion of which being terminal phenyl; Q is ##STR17## R₁is H, alkyl or aryl; R' is H, alkyl, aralkyl, hydrogen, nitro, carbonylor carboxaldehyde; n is an integer of from 1-15; and Y is H.
 2. Achelating agent in accordance with claim 1 wherein Z is CH₃, dodecyl, orcyclododecyl, Y is hydrogen, R₁ is hydrogen or methyl, and R' ishydrogen or nitro.
 3. A chelating agent in accordance with claim 1 ofthe formula ##STR18##
 4. A composition of matter of the formula##STR19## wherein Z is alkyl or aralkyl, the aliphatic portion of whichbeing long-chain alkyl and the aryl portion of which being a terminalphenyl; R₁ is H, alkyl or aryl; and R" is H, alkyl or aryl.